Pterocarpan synthase (PTS) structures suggest a common quinone methide–stabilizing function in dirigent proteins and proteins with dirigent-like domains

Meng, Qingyan; Moinuddin, Syed A.; Kim, Sung-Jin; Bedgar, Diana L.; Costa, Michael A.; Thomas, Dennis G.; Young, Robert P.; Smith, Clyde A.; Cort, John R.; Davin, Laurence B.; Lewis, Norman G.

doi:10.1074/jbc.ra120.012444

Title: Pterocarpan synthase (PTS) structures suggest a common quinone methide–stabilizing function in dirigent proteins and proteins with dirigent-like domains

Journal Article · 20 June 2020 · Journal of Biological Chemistry

DOI: https://doi.org/10.1074/jbc.ra120.012444 · OSTI ID:1668325

Meng, Qingyan ^[1];

^[1]; Kim, Sung-Jin ^[1]; Bedgar, Diana L. ^[1]; Costa, Michael A. ^[1];

^[2];

^[2]; Smith, Clyde A. ^[3];

^[4];

^[1];

^[1]

Washington State Univ., Pullman, WA (United States). Inst. of Biological Chemistry
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Washington State Univ., Pullman, WA (United States). Inst. of Biological Chemistry; Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

The biochemical activities of dirigent proteins (DPs) give rise to distinct complex classes of plant phenolics. DPs apparently began to emerge during the aquatic-to-land transition, with phylogenetic analyses revealing the presence of numerous DP subfamilies in the plant kingdom. The vast majority (>95%) of DPs in these large multigene families still await discovery of their biochemical functions. Here, we elucidated the 3D structures of two pterocarpan-forming proteins with dirigent-like domains. Both proteins stereospecifically convert distinct diastereomeric chiral isoflavonoid precursors to the chiral pterocarpans, (–)- and (+)-medicarpin, respectively. Their 3D structures enabled comparisons with stereoselective lignan– and aromatic terpenoid–forming DP orthologs. Furthermore, each protein provides entry into diverse plant natural products classes, and our experiments suggest a common biochemical mechanism in binding and stabilizing distinct plant phenol–derived mono- and bis-quinone methide intermediates during different C–C and C–O bond–forming processes. These observations provide key insights into both their appearance and functional diversification of DPs during land plant evolution/adaptation. The proposed biochemical mechanisms based on our findings provide important clues to how additional physiological roles for DPs and proteins harboring dirigent-like domains can now be rationally and systematically identified.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER); National Institutes of Health (NIH)

Grant/Contract Number:: AC05-76RL01830; AC02-76SF00515

OSTI ID:: 1668325

Alternate ID(s):: OSTI ID: 1769485

Report Number(s):: PNNL-SA--150677

Journal Information:: Journal of Biological Chemistry, Journal Name: Journal of Biological Chemistry Journal Issue: 33 Vol. 295; ISSN 0021-9258

Publisher:: American Society for Biochemistry and Molecular BiologyCopyright Statement

Country of Publication:: United States

Language:: English

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59 BASIC BIOLOGICAL SCIENCES
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Dirigent
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Pterocarpan
X-ray crystallography
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Crystallography
Dimerization
Docking
Plant biochemistry
Plant defense
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Quinone methides

Title: Pterocarpan synthase (PTS) structures suggest a common quinone methide–stabilizing function in dirigent proteins and proteins with dirigent-like domains

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